E 365 – 99 Designation E 365 – 99 Standard Test Method for the Determination of Vanadium in Ferrovanadium and Vanadium Alloying Additives 1 This standard is issued under the fixed designation E 365; t[.]
Designation: E 365 – 99 Standard Test Method for the Determination of Vanadium in Ferrovanadium and Vanadium Alloying Additives1 This standard is issued under the fixed designation E 365; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision A number in parentheses indicates the year of last reapproval A superscript epsilon (e) indicates an editorial change since the last revision or reapproval Scope 1.1 This test method covers the chemical analysis of ferrovanadium, vanadium carbide, and vanadium-aluminum having chemical compositions within the following limits: Element Aluminum Carbon Chromium Manganese Silicon Vanadium E 882 Guide for Accountability and Quality Control in the Chemical Analysis Laboratory6 Significance and Use 3.1 These test methods for the chemical analysis of metals and alloys are primarily intended as referee methods to test such materials for compliance with compositional specifications, particularly those under the jurisdiction of ASTM Committee A1 on Steel, Stainless Steel, and Related Alloys, specifically Specification A 102 It is assumed that all who use these methods will be trained analysts capable of performing common laboratory procedures skillfully and safely It is expected that work will be performed in a properly equipped laboratory under appropriate quality control practices such as those described in Guide E 882 Concentration Range, % 0.01 to 65 0.01 to 20 0.01 to 0.01 to 0.05 to 10 25 to 90 1.2 The test methods in this standard are contained in the sections below: Sections Vanadium by the Permanganate Oxidation—Ferrous Ammonium Sulfate Titration Method to 15 Reagents 4.1 Reagents: 4.1.1 Purity of Reagents—Unless otherwise indicated, all reagents used in these test methods shall conform to the “Reagent Grade” Specifications of the American Chemical Society.7 Other chemicals may be used, provided it is first ascertained that they are of sufficiently high purity to permit their use without adversely affecting the expected performance of the determination, as indicated in the section on “Precision and Bias.” 4.1.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by Type II of Specification D 1193 1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use Specific hazard statements are given in Section and in special “Warning” paragraphs throughout these test methods Referenced Documents 2.1 ASTM Standards: A 102 Specification for Ferrovanadium2 D 1193 Specification for Reagent Water3 E 29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications4 E 32 Practices for Sampling Ferroalloys and Steel Additives for Determination of Chemical Composition5 E 50 Practices for Apparatus, Reagents, and Safety Precautions for Chemical Analysis of Metals5 E 173 Practice for Conducting Interlaboratory Studies of Methods for Chemical Analysis of Metals5 Hazards 5.1 For precautions to be observed in the use of certain reagents in these test methods, refer to Practices E 50 Sampling 6.1 For procedures for sampling the material, refer to Practices E 32 These test methods are under the jurisdiction of ASTM Committee E-1 on Analytical Chemistry for Metals, Ores, and Related Materials and are the direct responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys Current edition approved Dec 10, 1999 Published February 2000 Originally published as E 365– 72 T Last previous edition E 365 –90 (1995)e1 Annual Book of ASTM Standards Vol 01.02 Annual Book of ASTM Standards, Vol 11.01 Annual Book of ASTM Standards, Vol 14.02 Annual Book of ASTM Standards, Vol 03.05 Annual Book of ASTM Standards, Vol 03.06 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S Pharmaceutical Convention, Inc (USPC), Rockville, MD Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States E 365 12.4 Sodium Diphenylamine Sulfonate Indicator Solution (2 g/L): 12.4.1 Test Method A (Preparation from Barium Diphenylamine Sulfonate)—Dissolve 0.32 g of barium diphenylamine sulfonate in 100 mL of hot water Add 0.5 g of sodium sulfate (Na2SO4), stir, and filter through a fine paper to remove the BaSO4 Store in a dark-colored bottle 12.4.2 Test Method B (Preparation from Sodium Diphenylamine Sulfonate)—Dissolve 0.20 g of sodium diphenylamine sulfonate in 100 mL of water Store in a dark-colored bottle 12.5 Sodium Nitrite Solution (10 g/L)—Dissolve 10 g of sodium nitrite (NaNO2) in water and dilute to L 12.6 Urea (NH 2CONH2) Rounding Calculated Values 7.1 Calculated values shall be rounded to the desired number of places as directed in 3.4 to 3.6 of Practice E 29 Interlaboratory Studies 8.1 These methods have been evaluated in accordance with Practice E 173 unless otherwise noted in the precision and bias section VANADIUM BY THE PERMANGANATE OXIDATION—FERROUS AMMONIUM SULFATE TITRATION TEST METHOD Scope 9.1 This test method covers the determination of vanadium in ferrovanadium, vanadium carbide, and vanadium-aluminum in concentrations from 25 to 75 % 13 Procedure 13.1 Transfer a 0.50-g sample, weighed to the nearest 0.1 mg, to a 600-mL beaker Add 50 mL of H2SO4(1 + 1), 30 mL of HNO3, and to drops of HF (Note 1) Cover the beaker and heat at 85 to 100°C until dissolution is complete Evaporate to the first fumes of H2SO4(Note 2) Cool, add 10 mL of H3PO4, dilute to 300 mL, and heat at 70 to 90°C until soluble salts are dissolved 10 Summary of Test Method 10.1 Vanadium in a sulfuric acid solution is oxidized at room temperature to V(+V) state by potassium permanganate The excess permanganate ions are reduced with sodium nitrite and the excess nitrite is destroyed by urea Vanadium is then titrated with ferrous ammonium sulfate to the V(+V) state with sodium diphenylamine sulfonate as the indicator NOTE 1—When the silicon concentration is greater than 1%, increase the amount of HF to to mL NOTE 2—Excessive fuming will make dissolution of the salts difficult 11 Interferences 11.1 The elements ordinarily present not interfere if their concentrations are under the maximum limits shown in 1.1 13.2 Add KMnO4 solution to the hot solution, while stirring, until a deep pink color persists, and then boil Cool to 15°C or less 12 Reagents 12.1 Ferrous Ammonium Sulfate Standard Solution (0.1 N)—Dissolve 39.2 g of ferrous ammonium sulfate (Fe(NH4) (SO4)2·H2O) in 500 mL of cold H2SO4(5 + 95) and dilute to L with H2SO4(5 + 95) Standardize the solution as follows: Using a pipet, transfer 50 mL of 10 N potassium dichromate solution to a 600-mL beaker containing 280 mL of water to which 10 mL of H2SO4(1 + 1), 10 mL of H3PO4, and 1.0 mL of sodium diphenylamine sulfonate solution have been added Using a 100-mL buret, titrate with the ferrous ammonium sulfate solution while stirring As the end point is approached, add the titrant dropwise Finally, add fractions of a drop by rinsing the tip of the buret with a stream of water from a wash bottle after forming a partial drop Continue the titration until the color changes from blue to green Record the buret reading to the nearest 0.05 mL Calculate the normality of the ferrous ammonium sulfate solution as follows: Normality 0.1 A/B TABLE Statistical Information Permanganate Oxidation-Ferrous Ammonium Sulfate Titration Test Method—Vanadium Test Specimen Ferrovanadium (Nominal: 30 V) Vanadium-Aluminum (Nominal: 50 V, 50 A1) Ferrovanadium (BAS No 205/3, 54.9 V) Ferrovanadium (Nominal: 70 V) Vanadium Found % Repeatability (R1, E173) Reproducibility (R2, E173) 28.27 0.15 0.42 51.73 0.30 0.42 54.94 0.18 0.63 71.99 0.32 0.51 13.3 Add rapidly, while stirring, 0.1 N ferrous ammonium sulfate solution until the solution is bright blue with no trace of green color (Note 3) Add KMnO4 solution, while stirring, until the solution remains a deep pink color, and continue stirring for Add NaNO2 solution dropwise, while stirring, until the solution is clear yellow, and then add mL in excess Immediately add g of urea and stir for Add 1.0 mL of sodium diphenylamine sulfonate solution Using a 100-mL buret, titrate with 0.1 N ferrous ammonium sulfate solution while stirring As the end point is approached, add the titrant dropwise; finally add fractions of a drop by rinsing the tip of the buret with a stream of water from a wash bottle after forming a partial drop Continue the titration until the color changes from blue to green Notes and Record the buret reading to the nearest 0.05 mL (1) where: A millilitres of 0.1 N K2Cr2O7 solution, and B millilitres of ferrous ammonium sulfate solution 12.2 Potassium Dichromate Standard Solution (0.1000 N)—Dissolve 4.90315 g of primary standard grade potassium dichromate (K2Cr 2O7) in water, transfer to a 1-L volumetric flask, dilute to volume, and mix This is a primary standard solution 12.3 Potassium Permanganate Solution (20 g/L)—Dissolve 20 g of potassium permanganate (KMnO 4) in water and dilute to L NOTE 3—An excess of a few millilitres in this preliminary reduction is of no consequence Do not record the volume used E 365 15 Precision and Bias 15.1 Precision—Nine laboratories cooperated in testing this method and obtained the data summarized in Table 15.2 Bias—No information on the accuracy of this test method is available The user is cautioned to verify, by the use of reference materials, if available, that the precision and bias of this method is adequate for the contemplated use NOTE 4—Titration on a white surface with a light in back of the beaker makes the end point easier to detect NOTE 5—The color change, while fairly sharp, is from dark blue through light blue to clear green 14 Calculation 14.1 Calculate the percentage of vanadium as follows: Vanadium, % @A B3 0.050942#/C 100 (2) 16 Keywords 16.1 chemical analysis; ferrovanadium; vanadium alloying additives where: A millilitres of ferrous ammonium sulfate solution, B normality of the ferrous ammonium sulfate solution, and C grams of sample used Supporting data are available from ASTM Headquarters Request RR: E031000 The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility This 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